CN112250053A - Method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid - Google Patents
Method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid Download PDFInfo
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- CN112250053A CN112250053A CN202011039726.8A CN202011039726A CN112250053A CN 112250053 A CN112250053 A CN 112250053A CN 202011039726 A CN202011039726 A CN 202011039726A CN 112250053 A CN112250053 A CN 112250053A
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- iron phosphate
- waste liquid
- etching waste
- ferric trichloride
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- 239000007788 liquid Substances 0.000 title claims abstract description 64
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 53
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 47
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 title claims abstract description 42
- 238000005530 etching Methods 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 15
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 239000010406 cathode material Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 6
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 8
- -1 hydrogen ions Chemical class 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- 229910001447 ferric ion Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid, which comprises the following steps: adding a material containing the simple substance iron into the ferric trichloride etching waste liquid for reaction to obtain a solution containing ferrous chloride, then adding an alkaline precipitator to obtain a clear liquid, adding the clear liquid into phosphoric acid, adding hydrogen peroxide under stirring, controlling the pH value with ammonia water, stirring and reacting at a certain temperature to obtain a precipitate, washing, drying and crushing to obtain the battery-grade iron phosphate. The method adopts the ferric trichloride etching waste liquid as the raw material to prepare the battery-grade ferric phosphate, has simple operation and low cost, and the obtained battery-grade ferric phosphate can be used for preparing the lithium iron phosphate cathode material of the lithium ion battery, can reduce the cost and improve the economic benefit while meeting the performance requirement of the lithium ion battery cathode material, and is beneficial to the recycling of resources.
Description
Technical Field
The invention relates to the technical field of preparation of battery-grade iron phosphate, in particular to a method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid.
Background
In the surface processing processes of printing, carving and the like of stainless steel, ferric trichloride solution is widely used as an etching agent. The ferric trichloride solution can continuously generate black brown ferric trichloride etching waste liquid in the stainless steel etching process, and generally, the components of the waste liquid mainly comprise: the mass fraction of ferric ions is about 8 percent, the mass fraction of ferrous ions is about 4 percent, the mass fraction of hydrogen chloride is about 3 percent, and the content of chromium is more than 5000 mg/L. The conventional treatment method of the etching waste liquid is generally direct neutralization discharge, the pH of the solution is adjusted by lime, heavy metal ions in the solution form hydroxide precipitate, and then the hydroxide precipitate is filtered and removed, a large amount of alkali is consumed, and a large amount of sludge containing iron and chromium metals is generated, so that not only is the environmental hazard caused, but also the resource is greatly wasted, and the treatment cost is high. Therefore, how to reasonably recycle the ferric trichloride etching waste liquid becomes the focus of the current research.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid.
The invention provides a method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid, which comprises the following steps:
s1, adding the material containing the simple substance iron into the ferric trichloride etching waste liquid, and completely reacting at 60-90 ℃ to obtain a solution containing ferrous chloride;
s2, adding an alkaline precipitator into the solution containing the ferrous chloride, stirring until no precipitate is generated, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a clear liquid;
s3, adding the clear liquid into phosphoric acid, adding hydrogen peroxide under stirring, controlling the reaction pH to be 1.5-2.5 by ammonia water, stirring at normal temperature for reaction till the reaction is complete, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a precipitate;
and S4, washing, drying and crushing the precipitate to obtain the battery-grade iron phosphate.
Preferably, in the step S1, the ratio of the mole number of the elemental iron in the elemental iron-containing material to the total mole number of the ferric iron ions and the hydrogen ions in the ferric trichloride etching waste liquid is more than 1: 2; the material containing the simple substance iron is at least one of iron sheets, iron powder and scrap iron.
Preferably, in the step S1, the material containing the elemental iron is added into the ferric trichloride etching waste liquid, and reacts at 60-90 ℃ until no gas is generated, and then continues to react for 1-3h to obtain a solution containing ferrous chloride.
Preferably, the alkaline precipitant is sodium hydroxide, sodium carbonate, or a combination thereof.
Preferably, in step S2, the ratio of the number of moles of phosphoric acid to the number of moles of hydrogen peroxide to the number of moles of ferrous ions in the clear liquid is 1: (0.5-0.51): (0.98-1).
Preferably, in step S4, the pH is washed to be weakly acidic, preferably 5.5 to 6.5.
Preferably, in step S4, the drying specifically includes: firstly, carrying out flash evaporation, air blast drying or spray drying treatment, and then dehydrating for 2-8h at the temperature of 350-430 ℃.
Preferably, in step S4, the pulverization is to a particle size of: d50 is more than or equal to 1 mu m and less than or equal to 5 mu m, and D100 is more than or equal to 45 mu m.
A battery grade iron phosphate made by the method.
The application of the battery-grade ferric phosphate in the preparation of lithium iron phosphate cathode materials of lithium ion batteries is provided.
Preferably, the preparation method of the lithium iron phosphate cathode material of the lithium ion battery comprises the following steps: mixing iron phosphate, a lithium source and a carbon source, preparing a precursor by adopting a sol-gel method, a hydrothermal method, a coprecipitation method or a solid phase method, and sintering in an inert atmosphere to prepare a lithium iron phosphate cathode material of the lithium ion battery; preferably, the ratio of the number of moles of iron phosphate to the number of moles of lithium element in the lithium source is 1: (1.001-1.05), wherein the mass ratio of the iron phosphate to the carbon source is 1: (0.01-0.1); preferably, the carbon source is at least one of glucose, sucrose and citric acid; preferably, the sintering is carried out for 5-12h at the temperature of 600-800 ℃ under the atmosphere of high-purity nitrogen or high-purity argon.
The invention has the following beneficial effects:
the invention firstly reduces the content of ferric ions and hydrogen ions in the ferric trichloride etching waste liquid through simple substance iron, improves the content of ferrous ions in the solution, and then adds alkaline precipitator to remove the residual impurity ions (Fe) in the solution3+，H+，Cr3+) And adding phosphoric acid and hydrogen peroxide, adjusting the pH value by ammonia water, and preparing the battery-grade iron phosphate by an oxidation precipitation method. Compared with the method for directly neutralizing and discharging the ferric trichloride etching waste liquid, the method for preparing the battery-grade ferric phosphate by using the ferric trichloride etching waste liquid as the raw material reduces the use amount of an alkaline precipitator and Cl-The discharge of (2) can reduce the environmental protection cost of the waste etching solution, reduce heavy metal pollution, reduce the harm to the environment, and the method is simple in operation, low in cost, high in yield and purity of the iron phosphate, and the obtained iron phosphate can be used for preparing the lithium iron phosphate anode material of the lithium ion battery, can reduce the cost while meeting the performance requirement of the lithium ion battery anode material, improves the economic benefit, and is favorable for recycling resources.
Drawings
Fig. 1 is an XRD pattern of the battery grade iron phosphate prepared in example 1 of the present invention.
Figure 2 is an SEM image of battery grade iron phosphate made in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid comprises the following steps:
s1, adding the iron sheet into the ferric trichloride etching waste liquid, reacting at 80 ℃ until no gas is generated, and continuing to react for 2.5h to obtain the ferric trichloride etching waste liquidA solution containing ferrous chloride, wherein the ratio n (Fe) of the mole number of elementary iron in iron pieces to the total mole number of ferric ions and hydrogen ions in the ferric chloride etching waste solution: n (Fe)3++H+) Is 1.1: 2;
s2, adding sodium carbonate into the solution containing the ferrous chloride, stirring until no precipitate is generated, and carrying out solid-liquid separation on the obtained reaction liquid to obtain clear liquid;
s3, adding the clear liquid into phosphoric acid, adding hydrogen peroxide under stirring, controlling the pH value of the reaction to be 1.9 by ammonia water, stirring the reaction solution at normal temperature until the reaction is completed, and carrying out solid-liquid separation on the obtained reaction solution to obtain a precipitate, wherein the ratio n (H) of the mole number of the phosphoric acid, the mole number of the hydrogen peroxide and the mole number of ferrous ions in the clear liquid is3PO4):n(H2O2)：n(Fe2+)＝1：0.505：0.99；
S4, washing the precipitate to pH 5.9, performing flash evaporation drying treatment, dehydrating at 395 ℃ for 4 hours, and crushing to obtain a particle size: d50 is less than or equal to 5 mu m, and D100 is less than or equal to 45 mu m, thus obtaining the battery-grade iron phosphate.
The battery grade iron phosphate prepared above was tested and the results are shown in table 1:
table 1 test results for battery grade iron phosphate
| Purity of | Fe/P(mol) | pH | Specific surface area (m)2/g) | Cr(ppm) | D50(μm) | D100(μm) | |
| Iron phosphate | 99.7％ | 0.979 | 3.48 | 4.3 | 18 | 3.45 | 18.66 |
The XRD characterization results of the above battery grade iron phosphate are shown in fig. 1, and the SEM characterization results are shown in fig. 2.
The lithium iron phosphate cathode material of the lithium ion battery is prepared by taking the battery-grade iron phosphate as a raw material, and the specific method comprises the following steps:
uniformly mixing iron phosphate, lithium carbonate and glucose, wherein the ratio of the mole number of the iron phosphate to the mole number of lithium elements in the lithium carbonate is 1: 1.01, wherein the mass ratio of the ferric phosphate to the glucose is 1: 0.1, preparing a precursor by a carbothermic method, and sintering in a high-purity nitrogen atmosphere to obtain the lithium iron phosphate anode material of the lithium ion battery, wherein the sintering temperature is 760 ℃, and the sintering time is 11 hours.
Example 2
A method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid comprises the following steps:
s1, adding iron powder into the ferric trichloride etching waste liquid, reacting at 60 ℃ until no gas is generated, and continuing to react for 3 hours to obtain a solution containing ferrous chloride, wherein the ratio n (Fe) of the mole number of the simple substance iron in the iron powder to the total mole number of ferric ions and hydrogen ions in the ferric trichloride etching waste liquid: n (Fe)3++H+)＝1.5：2；
S2, adding sodium hydroxide into the solution containing the ferrous chloride, stirring for reaction until no precipitate is generated, and carrying out solid-liquid separation on the obtained reaction liquid to obtain clear liquid;
s3, adding the clear liquid into phosphoric acid, adding hydrogen peroxide under stirring, controlling the pH value of the reaction to be 1.5 by ammonia water, stirring the reaction solution at normal temperature until the reaction is completed, and carrying out solid-liquid separation on the obtained reaction solution to obtain a precipitate, wherein the ratio n (H) of the mole number of the phosphoric acid, the mole number of the hydrogen peroxide and the mole number of ferrous ions in the clear liquid is3PO4):n(H2O2)：n(Fe2+)＝1：0.5：0.98；
S4, washing the precipitate to pH 5.5, then carrying out air-blast drying treatment, dehydrating at 350 ℃ for 8h, and crushing to obtain the following powder with the particle size: d50 is more than or equal to 1 mu m and less than or equal to 5 mu m, D100 is more than or equal to 45 mu m, and the battery-grade iron phosphate is obtained and has the purity of 99.8 percent.
Example 3
A method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid comprises the following steps:
s1, adding iron sheets and iron powder into the ferric trichloride etching waste liquid, reacting at 90 ℃ until no gas is generated, and continuing to react for 1h to obtain a solution containing ferrous chloride, wherein the ratio n (Fe) of the mole number of the simple substance iron in the iron sheets and the iron powder to the total mole number of ferric ions and hydrogen ions in the ferric trichloride etching waste liquid: n (Fe)3++H+)＝1.8：2；
S2, adding a mixture of sodium hydroxide and sodium carbonate into the solution containing ferrous chloride, stirring for reaction until no precipitate is generated, and carrying out solid-liquid separation on the obtained reaction solution to obtain a clear solution;
s3, adding the clear liquid into phosphoric acid, adding hydrogen peroxide under stirring, controlling the pH to 2.5 by ammonia water, stirring at normal temperature for reaction until the reaction is complete, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a precipitate, wherein the ratio n (H) of the mole number of the phosphoric acid, the mole number of the hydrogen peroxide and the mole number of the ferrous ions in the clear liquid is3PO4):n(H2O2)：n(Fe2+)＝1：0.51：1；
S4, washing the precipitate to pH 6.5, then carrying out spray drying treatment, dehydrating at 430 ℃ for 2h, and crushing to obtain a particle size: d50 is more than or equal to 1 mu m and less than or equal to 5 mu m, D100 is more than or equal to 45 mu m, and the battery-grade iron phosphate is obtained and has the purity of 99.6 percent.
Comparative example 1
A method of preparing battery grade iron phosphate comprising the steps of:
s1, adding the iron sheet into the ferric trichloride solution, reacting at 80 ℃ until no gas is generated, and continuing to react for 2.5h to obtain a solution containing ferrous chloride, wherein the ratio n (Fe) of the mole number of the simple substance iron in the iron sheet to the mole number of the ferric ion in the ferric trichloride solution: n (Fe)3+) Is 1.1: 2;
s2, adding the solution containing ferrous chloride into phosphoric acid, adding hydrogen peroxide while stirring, controlling the pH value of the reaction to be 1.9 by ammonia water, stirring the reaction at normal temperature until the reaction is completed, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a precipitate, wherein the ratio n (H) of the mole number of the phosphoric acid, the mole number of the hydrogen peroxide and the mole number of the ferrous ions in the solution containing the ferrous chloride3PO4):n(H2O2)：n(Fe2+)＝1：0.505：0.99；
S3, washing the precipitate to pH 5.9, performing flash evaporation drying treatment, dehydrating at 395 ℃ for 4 hours, and crushing to obtain a particle size: d50 is less than or equal to 5 mu m, and D100 is less than or equal to 45 mu m, thus obtaining the battery-grade iron phosphate.
The method for preparing the lithium iron phosphate cathode material of the lithium ion battery by using the prepared battery-grade iron phosphate as the raw material is the same as that of the embodiment 1.
The lithium iron phosphate positive electrode materials of the lithium ion batteries prepared in example 1 and comparative example 1 were subjected to performance tests, and the results are shown in table 2:
table 2 lithium ion battery lithium iron phosphate positive electrode material performance test results
As can be seen from table 2, the electrochemical performance of the battery-grade iron phosphate obtained by the method of the present invention is equivalent to that of the battery-grade iron phosphate prepared from a pure ferric chloride solution, and the performance requirements of the lithium iron phosphate positive electrode material can be satisfied.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for preparing battery-grade iron phosphate by using ferric trichloride etching waste liquid is characterized by comprising the following steps:
s1, adding the material containing the simple substance iron into the ferric trichloride etching waste liquid, and completely reacting at 60-90 ℃ to obtain a solution containing ferrous chloride;
s2, adding an alkaline precipitator into the solution containing the ferrous chloride, stirring until no precipitate is generated, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a clear liquid;
s3, adding the clear liquid into phosphoric acid, adding hydrogen peroxide under stirring, controlling the reaction pH to be 1.5-2.5 by ammonia water, stirring at normal temperature for reaction till the reaction is complete, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a precipitate;
and S4, washing, drying and crushing the precipitate to obtain the battery-grade iron phosphate.
2. The method for preparing battery-grade iron phosphate from the ferric trichloride etching waste liquid according to claim 1, wherein in the step S1, the ratio of the mole number of the elemental iron in the elemental iron-containing material to the total mole number of the ferric ions and the hydrogen ions in the ferric trichloride etching waste liquid is more than 1: 2; the material containing the simple substance iron is at least one of iron sheets, iron powder and scrap iron.
3. The method for preparing battery-grade iron phosphate by using the ferric trichloride etching waste liquid according to claim 1 or 2, wherein in the step S1, the material containing the elemental iron is added into the ferric trichloride etching waste liquid, and reacts at 60-90 ℃ until no gas is generated, and then continues to react for 1-3h to obtain the solution containing the ferrous chloride.
4. The method for preparing battery-grade iron phosphate by using the ferric trichloride etching waste liquid according to any one of claims 1 to 3, wherein the alkaline precipitator is sodium hydroxide, sodium carbonate or a combination thereof.
5. The method for preparing battery-grade iron phosphate from the ferric trichloride etching waste liquid according to any one of claims 1 to 4, wherein in the step S2, the ratio of the mole number of the phosphoric acid, the mole number of the hydrogen peroxide and the mole number of the ferrous ions in the clear liquid is 1: (0.5-0.51): (0.98-1).
6. The method for preparing battery-grade iron phosphate by using the ferric trichloride etching waste liquid according to any one of claims 1 to 5, wherein in the step S4, the washing is carried out until the pH value is weakly acidic, preferably 5.5 to 6.5.
7. The method for preparing battery-grade iron phosphate by using the ferric trichloride etching waste liquid according to any one of claims 1 to 6, wherein in the step S4, the drying specifically comprises the following steps: firstly, carrying out flash evaporation, air blast drying or spray drying treatment, and then dehydrating for 2-8h at the temperature of 350-430 ℃.
8. The method for preparing battery-grade iron phosphate by using the ferric trichloride etching waste liquid according to claim 1, wherein in the step S4, the ferric phosphate is crushed to a particle size of: d50 is more than or equal to 1 mu m and less than or equal to 5 mu m, and D100 is more than or equal to 45 mu m.
9. A battery grade iron phosphate made by the method of any one of claims 1 to 8.
10. Use of the battery grade iron phosphate according to claim 9 in the preparation of lithium iron phosphate cathode materials for lithium ion batteries.
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| CN113955732A (en) * | 2021-11-12 | 2022-01-21 | 斯瑞尔环境科技股份有限公司 | Method for preparing iron phosphate by using ferric trichloride as catalyst |
| CN115385507A (en) * | 2022-09-01 | 2022-11-25 | 大连东泰产业废弃物处理有限公司 | Pretreatment method for co-processing of waste etching liquid of sulfuric acid system and water treatment chromium-containing sludge |
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